This study introduces an innovative method for synthesizing Cadmium Oxide /Cadmium Sulfide/Zinc Oxide heterostructures (CdO/CdS/ZnO), emphasizing their potential application in solar energy. Utilizing a combination of electrochemical deposition and oxygen annealing, the research provides a thorough analysis of the heterostructures through scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD), Raman spectroscopy, and photoluminescence (PL) spectroscopy. The findings reveal a complex surface morphology and a composite structure with significant contributions from hexagonal CdS and cubic CdO phases. The study highlights the uniformity in the distribution of luminescent centers and the crystalline quality of the heterostructures, which is evident from the PL analysis. The redshift observed in the emission peak and the additional peaks in the excitation spectrum indicate intricate optical properties influenced by various factors, including quantum confinement and lattice strain. The research demonstrates these heterostructures’ potential in enhancing solar cells’ efficiency and applicability in optoelectronic devices. This comprehensive characterization and analysis pave the way for future optimization and application in efficient and sustainable solar energy solutions.